CN110898845A - Preparation method of graphene modified hydrothermally synthesized ruthenium oxide-cerium oxide composite electrode - Google Patents
Preparation method of graphene modified hydrothermally synthesized ruthenium oxide-cerium oxide composite electrode Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 11
- QDHMHZMOYFOGQK-UHFFFAOYSA-N [O-2].[Ce+3].[Ru+]=O.[O-2] Chemical compound [O-2].[Ce+3].[Ru+]=O.[O-2] QDHMHZMOYFOGQK-UHFFFAOYSA-N 0.000 title description 2
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- 239000000203 mixture Substances 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 23
- 229940012189 methyl orange Drugs 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 7
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- WEDXVUHOBZDVHR-UHFFFAOYSA-N cerium(3+) oxygen(2-) ruthenium(3+) Chemical compound [O-2].[Ce+3].[Ru+3].[O-2].[O-2] WEDXVUHOBZDVHR-UHFFFAOYSA-N 0.000 abstract description 14
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Abstract
The invention belongs to the technical field of photoelectrocatalysis degradation of organic solution, and particularly relates to graphene modified hydrothermal synthesis RuO2‑CeO2And (3) researching the composite electrode and the photoelectric catalytic performance thereof. According to the invention, the ruthenium cerium oxide synthesized by a hydrothermal method is doped with graphene, the conductivity of the electrode material is improved by controlling the addition amount of the graphene, and the efficient utilization of photons in photocatalysis and the generation and separation of photon-generated carriers are facilitated, so that the photoelectrocatalysis performance of the electrode material is improved. The prepared electrode can be used for simulating photoelectrocatalysisThe experiment for chemically degrading the organic wastewater has a great practical application value.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis degradation of organic solution, and particularly relates to graphene modified hydrothermal synthesis RuO2-CeO2A composite electrode and application thereof in the aspect of photoelectrocatalysis degradation of organic solution.
Background
At present, cerium dioxide is widely applied and can be used in various industries as a luminescent material, a catalyst, an ultraviolet absorbent and the like. Meanwhile, there are many kinds of cerium-based catalysts, including CeO2Catalysts in which the carrier is loaded with a metal or noble metal, e.g. CuO/CeO2、Au/ CeO2And the like. The doped noble metal can introduce an impurity energy level into the semiconductor, so that photons with smaller energy can excite electrons on the impurity energy level, thereby improving the utilization rate of the photons; defects can be formed in the crystal, the migration rate of photon-generated carriers is improved, and the recombination of photon-generated electrons and holes is inhibited. Graphene as SP2The hybrid conductor has the characteristics of good electric and heat conducting properties, large surface area, stable structure and the like. Therefore, doping graphene decreases the band gap of the semiconductor, increases the specific surface area, improves the conductivity, and improves the catalytic degradation efficiency of the semiconductor.
The powder prepared by the hydrothermal synthesis method has the advantages of small granularity, uniform distribution, complete grain development, weaker agglomeration among particles and the like, so that the catalyst prepared by the method has obvious advantages in the aspect of catalytic degradation of organic solution. In recent years, the photoelectrocatalysis technology attracts attention by its unique photoelectricity synergistic effect and high efficiency catalytic efficiency, and has remarkable effect in degrading organic solution.
Disclosure of Invention
The invention aims to provide graphene modified hydrothermal synthesis RuO2-CeO2A preparation method of the composite electrode and a research on the photoelectric catalytic performance of the composite electrode. The invention adopts a hydrothermal synthesis method to prepare ruthenium cerium oxide powder with uniform particles and weak agglomeration, then the ruthenium cerium oxide powder is dissolved in ethanol and added with graphene with different masses, and finally the graphene modified hydrothermal synthesis RuO is obtained2-CeO2And (3) a composite electrode. The doped graphene can reduce the band gap width of a semiconductor, expand the photoresponse range, improve the specific surface area of the electrode and increase the adsorption quantity of the electrode surface to degradation substances. After verification, the following steps are carried out: the electrode has higher photoelectrocatalysis degradation efficiency to methyl orange solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
graphene modified hydrothermal synthesis RuO2-CeO2The preparation method of the composite electrode and the research on the photoelectric catalytic performance thereof comprise the following steps:
(1) mixing cerous nitrate hexahydrate and RuCl3Respectively dissolving the powder (containing 37wt% of ruthenium) in ethanol solution, and then adding 0.5-2 mol/L of Ce (NO)3)3Solution and 0.5-2 mol/L RuCl3Mixing the solutions to obtain a mixed solution containing ruthenium and cerium metal ions in a molar ratio of 1 (6-15);
(2) adding ammonia water into the mixed solution obtained in the step (1), and adjusting the pH value to 7-10; putting the mixture into a constant-temperature water bath kettle at the temperature of 50-80 ℃, and heating and stirring for 30-90 min; transferring the mixture into a hydrothermal reaction kettle, and reacting for 20-30 h at the temperature of 80-150 ℃ to obtain a precipitate;
(3) putting the precipitate obtained in the step (2) into a centrifuge for centrifugation, and then washing with ethanol and distilled water for 3-6 times respectively; putting the obtained solid matter into a drying box, and drying for 10-15 h at the temperature of 60-100 ℃; putting the dried solid matter into an agate mortar for grinding for 10-30 min; obtaining a solid powder;
(4) dissolving the solid powder obtained in the step (3) in ethanol to prepare a solution with the total concentration of ruthenium and cerium of 1-3 mol/L; then, ultrasonically vibrating for 10-30 min to uniformly disperse the particles;
(5) adding graphene with the final concentration of 0-30 mg/mL into the solution obtained in the step (4), and carrying out ultrasonic oscillation for 10-30 min to uniformly mix the graphene and the solution;
(6) taking the mixed solution obtained in the step (5), sucking 10-20 mu of the mixed solution by a liquid transfer gun each time, uniformly coating the mixed solution on the derusted and deoiled Ti, placing the coated Ti under an infrared lamp for drying for 10-30 min, placing the dried Ti in a muffle furnace at the temperature of 450-600 ℃ for pre-oxidation for 10-30 min, taking out and air-cooling; then repeating the coating, drying, pre-oxidizing and air cooling processes for 8-20 times; then placing the sample in a muffle furnace at 450-600 ℃ for annealing for 1-5 h; obtaining graphene modified hydrothermal synthesized RuO2-CeO2And (3) a composite electrode.
Graphene modified hydrothermally synthesized RuO2-CeO2The application of the composite electrode in the photoelectrocatalysis degradation of methyl orange solution comprises the following steps: weighing methyl orange and sodium sulfate powder, dissolving in deionized water, diluting to a constant volume of 1L, and preparing into methyl orange and Na with certain concentration2SO4Mixing the solution, preparing electrode as working electrode, and treating methyl orange and Na under irradiation of three-electrode system and UV xenon lamp2SO4The mixed solution was subjected to photocatalytic, electrocatalytic and photoelectrocatalytic degradation experiments.
The graphene modified hydrothermal synthesized RuO2-CeO2The composite electrode is applied to the photoelectrocatalysis degradation of methyl orange solution: preparing 20-40 mg/L methyl orange and 0.1-1 mol/L Na2SO4The mixed solution of (1); the range of the external applied voltage is 1-4.5V; the time of the photoelectrocatalysis on the methyl orange solution is 30-200 min.
The invention has the following remarkable advantages:
(1) the invention adopts hydrothermal synthesis method to prepare RuO2-CeO2The precursor of the composite electrode ensures that the generated ruthenium cerium oxide particles are uniform and have weaker agglomeration, thereby improving the catalytic performance of the electrode.
(2) Graphene modified hydrothermal synthesized RuO prepared by the invention2-CeO2Due to the addition of the graphene, the forbidden bandwidth of the semiconductor is reduced, so that photons with smaller energy can excite electrons on impurity levels, and the utilization rate of the photons is improved; meanwhile, the specific surface area of the electrode is increased by doping graphene, and the adsorption capacity of the electrode on degradation substances is increased, so that the degradation efficiency of the electrode is improved.
(3) The electrode prepared by the invention is doped with graphene on the basis of ruthenium-doped cerium dioxide, noble metal and graphene are used as electrocatalytic elements, cerium dioxide is used as a photocatalytic element, and under the conditions of external voltage and ultraviolet illumination, the two synergistically act to degrade methyl orange solution; the defects of low light utilization rate of pure photocatalysis, high energy consumption of pure electrocatalysis and the like are overcome.
Drawings
FIG. 1 shows RuO doped graphene with different concentrations under dark state (a) and light state (b) conditions corresponding to examples 1-52-CeO2Polarization curves of the composite electrode;
FIG. 2 shows examples 1-5 with different concentrations of graphene-modified RuO2-CeO2An alternating current impedance spectrum of the composite electrode;
FIG. 3 shows different concentrations of graphene-modified RuO according to examples 1-52-CeO2Degrading the ultraviolet-visible absorption spectrum of the methyl orange solution for 100min by the composite electrode under the photoelectrocatalysis condition;
FIG. 4 is an ultraviolet-visible absorption spectrum of a methyl orange solution degraded by the prepared electrode under a photocatalytic condition when the graphene doping concentration is 10 mg/mL;
FIG. 5 is an ultraviolet-visible absorption spectrum of a methyl orange solution degraded by a prepared electrode under an electrocatalytic condition when the graphene doping concentration is 10 mg/mL;
fig. 6 is an ultraviolet-visible absorption spectrum of a methyl orange solution degraded by the prepared electrode under the photoelectrocatalysis condition when the doping concentration of graphene is 10 mg/mL.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
RuO2-CeO2The preparation method of the composite electrode and the research on the photoelectric catalytic performance thereof comprise the following steps:
(1) dissolving cerous nitrate hexahydrate in ethanol solution to prepare 1mol/L Ce (NO)3)3A solution; adding RuCl3The powder (containing 37wt% of ruthenium) is dissolved in ethanol solution to prepare 1mol/L RuCl3A solution; then mixing according to the molar ratio of the ruthenium and cerium metal ions of 1:9.7 to obtain a mixed solution.
(2) Adding ammonia water into the mixed solution, and adjusting the pH value to 8; then putting the mixture into a constant-temperature water bath kettle, heating and stirring the mixture for 0.5h at the temperature of 80 ℃, then transferring the mixture into a hydrothermal reaction kettle, and reacting the mixture for 24 h at the temperature of 100 ℃; centrifuging the obtained precipitate on a centrifuge, washing with ethanol and distilled water for 3 times, placing into a crucible, and drying in an oven at 80 deg.C for 12 h; the obtained powder was put in an agate mortar and ground clockwise for 10min to obtain a ruthenium cerium oxide powder.
(3) Dissolving the ruthenium cerium oxide powder in ethanol to prepare a solution with the total concentration of ruthenium and cerium of 1mol/L, and uniformly dispersing the solution by ultrasonic oscillation.
(4) Uniformly coating 12 mu L of the obtained solution on a pretreated titanium plate by using a liquid transfer gun, placing the titanium plate under an infrared lamp for irradiating for 10min, then placing the titanium plate in a muffle furnace at 500 ℃ for pre-oxidation for 10min, discharging the titanium plate out of the furnace and cooling; repeating the coating-drying-pre-oxidizing-cooling process for 8 times, and finally annealing and insulating the sample in a muffle furnace at 500 ℃ for 1 h to obtain RuO2-CeO2And (3) a composite electrode.
Prepared RuO2-CeO2The application of the composite electrode in the photoelectrocatalysis degradation of methyl orange solution comprises the following steps: weighing methyl orange and sodium sulfate powder, dissolving in deionized water, diluting to a constant volume of 1L, and preparing 20mg/L methyl orange and 0.1mol/L Na2SO4Mixing the solution, preparing electrode as working electrode, and subjecting methyl orange and Na under external voltage of 2.5V and irradiation of ultraviolet xenon lamp2SO4And carrying out a photoelectrocatalysis degradation experiment on the mixed solution. Sampling at intervals of 20min until the methyl orange solution is nearly colorless in 100min, and performing ultraviolet-visible light test on the obtained sampleThe graph was analyzed.
Example 2
Graphene modified hydrothermal synthesis RuO2-CeO2The preparation method of the composite electrode and the research on the photoelectric catalytic performance thereof comprise the following steps:
(1) dissolving cerous nitrate hexahydrate in ethanol solution to prepare 1mol/L Ce (NO)3)3A solution; adding RuCl3The powder (containing 37wt% of ruthenium) is dissolved in ethanol solution to prepare 1mol/L RuCl3A solution; then mixing according to the molar ratio of the ruthenium and cerium metal ions of 1:9.7 to obtain a mixed solution.
(2) Adding ammonia water into the mixed solution, and adjusting the pH value to 8; then putting the mixture into a constant-temperature water bath kettle, heating and stirring the mixture for 0.5h at the temperature of 80 ℃, then transferring the mixture into a hydrothermal reaction kettle, and reacting the mixture for 24 h at the temperature of 100 ℃; centrifuging the obtained precipitate on a centrifuge, washing with ethanol and distilled water for 3 times, placing into a crucible, and drying in an oven at 80 deg.C for 12 h; the obtained powder was put in an agate mortar and ground clockwise for 10min to obtain a ruthenium cerium oxide powder.
(3) Dissolving ruthenium cerium oxide powder in ethanol to prepare a solution with the total concentration of ruthenium and cerium being 1mol/L, then adding graphene into the solution to ensure that the doping concentration of the graphene is 5mg/mL, and uniformly dispersing the graphene by ultrasonic oscillation.
(4) Uniformly coating 12 mu L of the obtained solution on a pretreated titanium plate by using a liquid transfer gun, placing the titanium plate under an infrared lamp for irradiating for 10min, then placing the titanium plate in a muffle furnace at 500 ℃ for pre-oxidation for 10min, discharging the titanium plate out of the furnace and cooling; repeating the coating-drying-pre-oxidation-cooling process for 8 times, and finally annealing and insulating the sample in a muffle furnace at 500 ℃ for 1 h to obtain the RuO modified by graphene and synthesized by hydrothermal method2-CeO2And (3) a composite electrode.
Prepared graphene modified hydrothermal synthesis RuO2-CeO2The application of the composite electrode in the photoelectrocatalysis degradation of methyl orange solution comprises the following steps: weighing methyl orange and sodium sulfate powder, dissolving in deionized water, diluting to a constant volume of 1L, and preparing 20mg/L methyl orange and 0.1mol/L Na2SO4Mixing the solution, preparing electrode as working electrode, and subjecting to methyl orange and methyl orange under external voltage of 2.5V and irradiation of ultraviolet xenon lampNa2SO4And carrying out a photoelectrocatalysis degradation experiment on the mixed solution. Samples were taken at 20min intervals until 100min of methyl orange solution was nearly colorless, and the resulting samples were subjected to uv-vis testing and plotted for analysis.
Example 3
Graphene modified hydrothermal synthesis RuO2-CeO2The preparation method of the composite electrode and the research on the photoelectric catalytic performance thereof comprise the following steps:
(1) dissolving cerous nitrate hexahydrate in ethanol solution to prepare 1mol/L Ce (NO)3)3A solution; adding RuCl3The powder (containing 37wt% of ruthenium) is dissolved in ethanol solution to prepare 1mol/L RuCl3A solution; then mixing according to the molar ratio of the ruthenium and cerium metal ions of 1:9.7 to obtain a mixed solution.
(2) Adding ammonia water into the mixed solution, and adjusting the pH value to 8; then putting the mixture into a constant-temperature water bath kettle, heating and stirring the mixture for 0.5h at the temperature of 80 ℃, then transferring the mixture into a hydrothermal reaction kettle, and reacting the mixture for 24 h at the temperature of 100 ℃; centrifuging the obtained precipitate on a centrifuge, washing with ethanol and distilled water for 3 times, placing into a crucible, and drying in an oven at 80 deg.C for 12 h; the obtained powder was put in an agate mortar and ground clockwise for 10min to obtain a ruthenium cerium oxide powder.
(3) Dissolving ruthenium cerium oxide powder in ethanol to prepare a solution with the total concentration of ruthenium and cerium being 1mol/L, then adding graphene into the solution to ensure that the doping concentration of the graphene is 10mg/mL, and uniformly dispersing the graphene by ultrasonic oscillation.
(4) Uniformly coating 12 mu L of the obtained solution on a pretreated titanium plate by using a liquid transfer gun, placing the titanium plate under an infrared lamp for irradiating for 10min, then placing the titanium plate in a muffle furnace at 500 ℃ for pre-oxidation for 10min, discharging the titanium plate out of the furnace and cooling; repeating the coating-drying-pre-oxidation-cooling process for 8 times, and finally annealing and insulating the sample in a muffle furnace at 500 ℃ for 1 h to obtain the graphene modified hydrothermal synthesis RuO2-CeO2And (3) a composite electrode.
Prepared graphene modified hydrothermal synthesis RuO2-CeO2The application of the composite electrode in the photoelectrocatalysis degradation of methyl orange solution comprises the following steps: weighing methyl orange and sodium sulfate powder, dissolving in deionized water, and making into a solution with a constant volume of 1LPreparing 20mg/L methyl orange and 0.1mol/L Na2SO4Mixing the solution, preparing electrode as working electrode, and subjecting methyl orange and Na under external voltage of 2.5V and irradiation of ultraviolet xenon lamp2SO4And carrying out a photoelectrocatalysis degradation experiment on the mixed solution. Samples were taken at 20min intervals until 100min of methyl orange solution was nearly colorless, and the resulting samples were subjected to uv-vis testing and plotted for analysis.
Example 4
Graphene modified hydrothermal synthesis RuO2-CeO2The preparation method of the composite electrode and the research on the photoelectric catalytic performance thereof comprise the following steps:
(1) dissolving cerous nitrate hexahydrate in ethanol solution to prepare 1mol/L Ce (NO)3)3A solution; adding RuCl3The powder (containing 37wt% of ruthenium) is dissolved in ethanol solution to prepare 1mol/L RuCl3A solution; then mixing according to the molar ratio of the ruthenium and cerium metal ions of 1:9.7 to obtain a mixed solution.
(2) Adding ammonia water into the mixed solution, and adjusting the pH value to 8; then putting the mixture into a constant-temperature water bath kettle, heating and stirring the mixture for 0.5h at the temperature of 80 ℃, then transferring the mixture into a hydrothermal reaction kettle, and reacting the mixture for 24 h at the temperature of 100 ℃; centrifuging the obtained precipitate on a centrifuge, washing with ethanol and distilled water for 3 times, placing into a crucible, and drying in an oven at 80 deg.C for 12 h; the obtained powder was put in an agate mortar and ground clockwise for 10min to obtain a ruthenium cerium oxide powder.
(3) Dissolving ruthenium cerium oxide powder in ethanol to prepare a solution with the total concentration of ruthenium and cerium being 1mol/L, then adding graphene into the solution to ensure that the doping concentration of the graphene is 15mg/mL, and uniformly dispersing the graphene by ultrasonic oscillation.
(4) Uniformly coating 12 mu L of the obtained solution on a pretreated titanium plate by using a liquid transfer gun, placing the titanium plate under an infrared lamp for irradiating for 10min, then placing the titanium plate in a muffle furnace at 500 ℃ for pre-oxidation for 10min, discharging the titanium plate out of the furnace and cooling; repeating the coating-drying-pre-oxidation-cooling process for 8 times, and finally annealing and insulating the sample in a muffle furnace at 500 ℃ for 1 h to obtain the hydrothermal synthesis RuO2-CeO2And (3) a composite electrode.
Modified hydrothermal synthesis of prepared grapheneRuO2-CeO2The application of the composite electrode in the photoelectrocatalysis degradation of methyl orange solution comprises the following steps: weighing methyl orange and sodium sulfate powder, dissolving in deionized water, diluting to a constant volume of 1L, and preparing 20mg/L methyl orange and 0.1mol/L Na2SO4Mixing the solution, preparing electrode as working electrode, and subjecting methyl orange and Na under external voltage of 2.5V and irradiation of ultraviolet xenon lamp2SO4And carrying out a photoelectrocatalysis degradation experiment on the mixed solution. Samples were taken at 20min intervals until 100min of methyl orange solution was nearly colorless, and the resulting samples were subjected to uv-vis testing and plotted for analysis.
Example 5
Graphene modified hydrothermal synthesis RuO2-CeO2The preparation method of the composite electrode and the research on the photoelectric catalytic performance thereof comprise the following steps:
(1) dissolving cerous nitrate hexahydrate in ethanol solution to prepare 1mol/L Ce (NO)3)3A solution; adding RuCl3The powder (containing 37wt% of ruthenium) is dissolved in ethanol solution to prepare 1mol/L RuCl3A solution; then mixing according to the molar ratio of the ruthenium and cerium metal ions of 1:9.7 to obtain a mixed solution.
(2) Adding ammonia water into the mixed solution, and adjusting the pH value to 8; then putting the mixture into a constant-temperature water bath kettle, heating and stirring the mixture for 0.5h at the temperature of 80 ℃, then transferring the mixture into a hydrothermal reaction kettle, and reacting the mixture for 24 h at the temperature of 100 ℃; centrifuging the obtained precipitate on a centrifuge, washing with ethanol and distilled water for 3 times, placing into a crucible, and drying in an oven at 80 deg.C for 12 h; the obtained powder was put in an agate mortar and ground clockwise for 10min to obtain a ruthenium cerium oxide powder.
(3) Dissolving ruthenium cerium oxide powder in ethanol to prepare a solution with the total concentration of ruthenium and cerium being 1mol/L, then adding graphene into the solution to ensure that the doping concentration of the graphene is 20mg/mL, and uniformly dispersing the graphene by ultrasonic oscillation.
(4) Uniformly coating 12 mu L of the obtained solution on a pretreated titanium plate by using a liquid transfer gun, placing the titanium plate under an infrared lamp for irradiating for 10min, then placing the titanium plate in a muffle furnace at 500 ℃ for pre-oxidation for 10min, discharging the titanium plate out of the furnace and cooling; the coating-drying-pre-oxidation-cooling process was repeated 8 times, and the sample was finally brought to 500 deg.CAnnealing and heat preservation in a muffle furnace for 1 h to obtain the hydrothermal synthesis RuO2-CeO2And (3) a composite electrode.
Prepared graphene modified hydrothermal synthesis RuO2-CeO2The application of the composite electrode in the photoelectrocatalysis degradation of methyl orange solution comprises the following steps: weighing methyl orange and sodium sulfate powder, dissolving in deionized water, diluting to a constant volume of 1L, and preparing 20mg/L methyl orange and 0.1mol/L Na2SO4Mixing the solution, preparing electrode as working electrode, and subjecting methyl orange and Na under external voltage of 2.5V and irradiation of ultraviolet xenon lamp2SO4And carrying out a photoelectrocatalysis degradation experiment on the mixed solution. Samples were taken at 20min intervals until 100min of methyl orange solution was nearly colorless, and the resulting samples were subjected to uv-vis testing and plotted for analysis.
FIG. 1 shows RuO doped graphene with different concentrations under dark state (a) and light state (b) conditions corresponding to examples 1-52-CeO2Polarization curve of the composite electrode. It can be seen from the graph that, under the dark state, as the graphene concentration increases, the response current of the electrode tends to increase first and then decrease, and when the graphene concentration is 10mg/mL, the increase rate of the response current of the electrode is fastest, and finally the optimal value is reached. Under the light state condition, the response current of the electrode with the graphene concentration of 10mg/mL is increased fastest and far exceeds the response current of the electrode with other concentrations, and the photoelectrocatalysis degradation effect of the electrode under the condition is predicted to be the best.
FIG. 2 shows examples 1-5 with different concentrations of graphene-modified RuO2-CeO2Ac impedance spectrum of the composite electrode. The graph shows that the conductivity of the electrode is gradually enhanced along with the increase of the concentration of the graphene, and the graphene has good conductivity, so that the moving rate of electrons can be improved, and the photo-generated electrons and holes can be separated in photocatalysis, so that the utilization rate of carriers is improved; the electrode with the graphene concentration of 20mg/mL has the best conductivity.
FIG. 3 shows different concentrations of graphene-modified RuO according to examples 1-52-CeO2And degrading the methyl orange solution by the composite electrode under the photoelectrocatalysis condition for 100min to obtain the ultraviolet-visible absorption spectrum. As can be seen from the figure, each electrode is paired with a methyl groupThe orange solution has good degradation effect, the degradation effect of the electrode with the graphene concentration of 10mg/mL on the methyl orange solution reaches the optimal value, and the effect of almost completely degrading the methyl orange solution is achieved after the methyl orange solution is degraded for 100 min.
Fig. 4, fig. 5, and fig. 6 are ultraviolet-visible absorption spectra of the prepared electrode degrading methyl orange solution under the conditions of photocatalysis, electrocatalysis, and photoelectrocatalysis when the doping concentration of graphene is 10mg/mL, respectively; the results show that: the electrode has poor degradation effect on the methyl orange solution under both photocatalysis and electrocatalysis conditions, and the photoelectrocatalysis degradation effect on the methyl orange solution is ideal, and the advantages and the synergistic effect of the two are considered, so that the ideal degradation effect is achieved.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and all technical solutions that fall under the spirit of the present invention are included in the scope of the present invention.
Claims (9)
1. Graphene modified hydrothermal synthesis RuO2-CeO2The preparation method of the composite electrode is characterized by comprising the following steps of:
(1) mixing cerous nitrate hexahydrate and RuCl3Dissolving the powders in ethanol solution, respectively, and adding Ce (NO)3)3Solution and RuCl3Mixing the solutions to obtain a mixed solution containing ruthenium and cerium metal ions;
(2) adding ammonia water into the mixed solution obtained in the step (1), and adjusting the pH value; putting into a constant-temperature water bath kettle, heating and stirring; then transferring the mixture into a hydrothermal reaction kettle, and reacting for several hours at a certain temperature to obtain a precipitate;
(3) putting the sediment obtained in the step (2) into a centrifuge for centrifugation, and then washing with ethanol and distilled water respectively; putting the obtained solid substance into an oven, and keeping a certain temperature for drying for several hours; putting the dried solid matter into an agate mortar for grinding for a plurality of minutes; obtaining a solid powder;
(4) dissolving the solid powder obtained in the step (3) in ethanol to prepare a solution with a certain concentration; then ultrasonically vibrating for a period of time to uniformly disperse the mixture;
(5) adding graphene into the solution obtained in the step (4), and uniformly mixing the graphene and the solution by ultrasonic oscillation;
(6) uniformly coating the single surface of the mixed solution obtained in the step (5) on a derusting and deoiling titanium plate, drying the titanium plate under an infrared lamp, placing the titanium plate in a muffle furnace at a certain temperature for pre-oxidation for a period of time, taking out the titanium plate and air-cooling; then repeating the coating-drying-pre-oxidizing-air cooling process for a plurality of times; then placing the sample in a muffle furnace at a certain temperature for annealing for several hours; obtaining graphene modified hydrothermal synthesized RuO2-CeO2And (3) a composite electrode.
2. The method of claim 1, wherein: ce (NO) in step (1)3)3And RuCl3The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the ruthenium and the cerium metal ions in the mixed solution is 1 (6-15).
3. The method of claim 1, wherein: adding ammonia water to adjust the pH value of the solution to 7-10 in the step (2), controlling the temperature of the constant-temperature water bath kettle to be 50-80 ℃, and heating and stirring for 30-90 min; the reaction temperature of the hydrothermal reaction kettle is 80-150 ℃, and the reaction time is 20-30 h.
4. The method of claim 1, wherein: washing the precipitate in the step (3) with ethanol and distilled water respectively for 3-6 times, wherein the temperature of an oven is 60-100 ℃, and the drying time is 10-15 h; the grinding time is 10-30 min.
5. The method of claim 1, wherein: in the step (4), the total concentration of the ruthenium and cerium elements in the solution prepared from the solid powder is 1-3 mol/L, and the ultrasonic oscillation time is 10-30 mins.
6. The method of claim 1, wherein: the final concentration of the added graphene in the step (5) is 0-30 mg/mL, and the ultrasonic oscillation time is 10-30 min.
7. The method of claim 1, wherein: in the step (6), the coating amount of each time of coating the single surface of the titanium plate is 10-20 mu L, and the coating times are 8-20 times; drying time of the infrared lamp is 10-30 min, pre-oxidation temperature in a muffle furnace is 450-600 ℃, pre-oxidation time is 10-30 min, and annealing time is 1-5 h.
8. Graphene modified hydrothermally synthesized RuO prepared by the preparation method according to any one of claims 1-72-CeO2The application of the composite electrode in treating organic solution under the photoelectric synergistic effect is characterized in that: hydrothermal synthesis of RuO by graphene modification2-CeO2The composite electrode is used as a working electrode, and methyl orange and Na are subjected to certain voltage pair under the irradiation of an ultraviolet lamp2SO4And carrying out photoelectrocatalysis degradation on the mixed solution.
9. Use according to claim 8, characterized in that: the concentration of methyl orange in the mixed solution is 20-40 mg/L, Na2SO4The concentration of the organic compound is 0.1-1 mol/L, the range of externally applied voltage is 1-4.5V, and the time of the photoelectrocatalysis on methyl orange is 30-200 min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142168A (en) * | 2020-09-18 | 2020-12-29 | 中国南方电网有限责任公司超高压输电公司天生桥局 | Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method |
| CN112174126A (en) * | 2020-08-31 | 2021-01-05 | 浙江工业大学 | RuO2·xH2Preparation method of O/graphene composite nano electrode material |
| CN113019364A (en) * | 2021-03-29 | 2021-06-25 | 西北有色金属研究院 | Preparation method of porous ruthenium dioxide-cerium dioxide microsphere composite material |
| CN113813974A (en) * | 2021-10-13 | 2021-12-21 | 福州大学 | Titanium carbide-Mxene doped modified photoelectrocatalysis electrode and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003024787A (en) * | 2001-04-25 | 2003-01-28 | Rohm & Haas Co | Mixed metal oxide catalyst |
| CN1900368A (en) * | 2006-06-30 | 2007-01-24 | 福州大学 | Titanium anode containing ruthenium coating of high cerium content and its preparing method |
| CN102500369A (en) * | 2011-10-31 | 2012-06-20 | 福州大学 | Active oxide material containing Ce and preparation method thereof |
| CN107275568A (en) * | 2017-07-04 | 2017-10-20 | 福州大学 | A kind of ruthenic oxide Quito pore electrod of graphene doping and preparation method thereof |
| CN107364933A (en) * | 2017-07-18 | 2017-11-21 | 王林双 | The preparation technology and graphene combination electrode of graphene combination electrode and its application |
| CN108998807A (en) * | 2018-06-28 | 2018-12-14 | 江苏安凯特科技股份有限公司 | A kind of improved Ru-Ce coated electrode |
| CN109651360A (en) * | 2018-12-19 | 2019-04-19 | 云南大学 | A kind of method that the compound gold of nano-cerium oxide prepares fibrauretine with ru oxide photocatalysis |
| CN110002547A (en) * | 2019-04-23 | 2019-07-12 | 福州大学 | A kind of the ruthenium Zirconium oxide electrode and its PhotoelectrocatalytiPerformance Performance of sol-gal process preparation |
-
2019
- 2019-12-21 CN CN201911331193.8A patent/CN110898845B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003024787A (en) * | 2001-04-25 | 2003-01-28 | Rohm & Haas Co | Mixed metal oxide catalyst |
| CN1900368A (en) * | 2006-06-30 | 2007-01-24 | 福州大学 | Titanium anode containing ruthenium coating of high cerium content and its preparing method |
| CN102500369A (en) * | 2011-10-31 | 2012-06-20 | 福州大学 | Active oxide material containing Ce and preparation method thereof |
| CN107275568A (en) * | 2017-07-04 | 2017-10-20 | 福州大学 | A kind of ruthenic oxide Quito pore electrod of graphene doping and preparation method thereof |
| CN107364933A (en) * | 2017-07-18 | 2017-11-21 | 王林双 | The preparation technology and graphene combination electrode of graphene combination electrode and its application |
| CN108998807A (en) * | 2018-06-28 | 2018-12-14 | 江苏安凯特科技股份有限公司 | A kind of improved Ru-Ce coated electrode |
| CN109651360A (en) * | 2018-12-19 | 2019-04-19 | 云南大学 | A kind of method that the compound gold of nano-cerium oxide prepares fibrauretine with ru oxide photocatalysis |
| CN110002547A (en) * | 2019-04-23 | 2019-07-12 | 福州大学 | A kind of the ruthenium Zirconium oxide electrode and its PhotoelectrocatalytiPerformance Performance of sol-gal process preparation |
Non-Patent Citations (2)
| Title |
|---|
| KUSMIEREK, ELZBIETA ET AL.: ""Use of the CeO2-modified Ti/TiO2-RuO2 electrodes in oxidation of Acid Orange 7"", 《PRZEMYSL CHEMICZNY》 * |
| 刘漫红 等编: "《纳米材料及其制备技术》", 31 August 2014, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174126A (en) * | 2020-08-31 | 2021-01-05 | 浙江工业大学 | RuO2·xH2Preparation method of O/graphene composite nano electrode material |
| CN112142168A (en) * | 2020-09-18 | 2020-12-29 | 中国南方电网有限责任公司超高压输电公司天生桥局 | Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method |
| CN112142168B (en) * | 2020-09-18 | 2022-06-03 | 中国南方电网有限责任公司超高压输电公司天生桥局 | Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method |
| CN113019364A (en) * | 2021-03-29 | 2021-06-25 | 西北有色金属研究院 | Preparation method of porous ruthenium dioxide-cerium dioxide microsphere composite material |
| CN113813974A (en) * | 2021-10-13 | 2021-12-21 | 福州大学 | Titanium carbide-Mxene doped modified photoelectrocatalysis electrode and preparation method thereof |
| CN113813974B (en) * | 2021-10-13 | 2023-08-11 | 福州大学 | Titanium carbide-Mxene doped modified photoelectrocatalysis electrode and preparation method thereof |
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